Estimation of the ionization potential for polyhalogenated hydrocarbons by weakest bound potential method

Abstract

The weakest bound potential method was proposed to estimate the ionization potential (IP) of polyhalogenated methanes, that is, the model IP = aχve + bPEIfi + c was developed, in which χve is molecular electronegativity calculated by valence electrons equilibration method, and polarizability effect index (PEI)fi is the influence of polarizability effect. The result indicates that the model is reasonable and effective to predict the IP for polyhalogenated methanes. Besides, the quantum chemistry method, the MOPAC AM1 method, and the density functional theory (B3LYP) method were employed to calculate the IP values of the same polyhalogenated methanes, and those results were less than that of the weakest bound potential method. Furthermore, the experimental values of 67 polyhalogenated hydrocarbons were correlated with the parameters χve and PEIfi. The regression results show a good correlation (R = 0.988), and the average absolute error between the experimental values and the calculated values is only 0.10 eV. Copyright © 2011 John Wiley & Sons, Ltd.

Group effect on ionization potential formono-substituted aliphatic compounds

“…The group descriptors and the correlation results are listed in Table and , respectively. In some previous researches, the calculation of IP values had been recommended to use with DFT(B3LYP) method. Therefore, the gaussian 03 software package (DFT method) is also employed to compute their IP values, and both geometry optimization and energy calculation are chosen to compute at B3LYP/6–31 + G(d, p) level.…”

Modified NPOH Equation Showing Terminal Effect: Boiling point of homologs monosubstituted alkanes (RX)

“…Take RH, ROH, and RBr for examples, their boiling points change as carbon atom number change, as shown in Figure 1. From Figure 1, two characteristics can be observed: (1) The boiling point of homologs increases with the increase of the number of carbon atom; (2) with the increase of the number of carbon atom, the boiling points of ROH and RBr gradually approach the boiling point of RH. This phenomenon can be explained as follows: The boiling point differences between RH and ROH, and RH and RBr originate from the influence of terminal groups OH and Br, respectively.…”

“…Therefore, the action way of substituent effect on the property of compounds is different from that in conjugated system. Wu et al [2][3][4] and Cao et al [5] proposed the weakest bound potential method and group interaction potential to study the ionization potential and enthalpy of formation of chain organic compounds, indicating that the polarization property and electronegativity of groups have unique effects on the properties of compounds.…”